Pad-dyeing and printing textile fibers



United States Patent 3,503,698 PAD-DYEING AND PRINTING TEXTILE FIBERS Jacques Zurbuchen, Pratteln, Basel-Land, Ernst Adolf Riiuchle, Base], and Jakob Bindler, Riehen, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland Continuation-impart of application Ser. No. 464,263, May 11, 1965, which is a division of application Ser. No. 409,349, Nov. 2, 1964, which in turn is a continuation-in-part of application Ser. No. 333,261, Dec. 23, 1963. This application Feb. 8, 1966, Ser. No. 525,937 Claims priority, application Switzerland, Feb. 8, 1963, 1,594/63; May 21, 1963, 6,325/63; July 22, 1964, 9,566/64; July 24, 1964, 9,705/64 Int. Cl. D06p /06; C11d N12 US. Cl. 8-41 26 Claims ABSTRACT OF THE DISCLOSURE There is disclosed a process for the continuous paddyeing of natural and synthetic polyamide and other textile fibers as well as novel dyestufi carriers and dyestuff pastes prepared therefrom. The process involves impregnating the fibers with an aqueous pad-liquor and fixing the dyestuff on the treated goods by a heat treatment in a humid medium, by treating the goods with hot steam and/or passing them through a hot acid bath. The padliquor contains a dyestutf carrier, non-cationic dyestuif capable of drawing on the fibers and sutficient additional adjuvants to achieve the proper pH and viscosity range. The dyestulf carrier consists essentially of a mixture of (A) An unsulfated amide of a member selected from the class consisting of wholly saturated fatty acid of from 8 to 14 carbon atoms, and lower alkaonic acid which is substituted by higher alkyl-phenoxy wherein the higher alkyl moiety has from 8 to 12 carbon atoms, amidified with a member selected from the group consisting of (a) mono-hydroxy and di-hydroxy substituted monoalkylamines of from 2 to 4 carbon atoms, having one hydroxyl group in w-position,

(b) bis-(w-hydroxyalkyl)-amines of a total of from 4 to 6 carbon atoms,

(c) N-lower alkyl-N-w-hydroxyalkylamine wherein the hydroxyalkyl group has from 2 to 3 carbon atoms, and

(d) mono-(w-alkoxy-alkyD-amine of a total of from 3 to 5 carbon atoms, at least two of which pertain to the alkyl moiety;

(B) A member selected from the group consisting of (i) a sulfated alkanol of from 8 to 14 carbon atoms,

(ii) a sulfated condensation product of an alkanol of from 8 to 14 carbon atoms with ethylene oxide, consensed with each other in a molar ratio of from 1:1 to 1:20,

(iii) a sulfated condensation product of alkylphenol, the

alkyl moiety of which has from 8 to 12 carbon atoms, with ethylene oxide, in a molar ratio of from 1:1 to 1:20,

(iv) a sulfated N-hydroxy-lower alkyl-substituted amide of a substantially wholly saturated fatty acid of from 8 to 14 carbon atoms,

(v) a sulfated (higher alkylphenoxy)-substituted lower alkanoic acid N-hydroxy-lower alkyl-substituted amide, wherein the higher alkyl group has from 8 to 12 carbon atoms,

(vi) a sulfated (higher alkylphenyl)-2,3-dihydroxypropyl)-ether the higher alkyl radical of which has from 8 to 12 carbon atoms,

(vii) a sulfated hydroxy-substituted unsaturated fatty acid or a lower alkyl ester thereof, said fatty acid having from 15 to 18 carbon atoms,

3,503,598 Patented Mar. 31, 1970 (viii) the alkali metal, ammonium, lower alkyl-ammonium and w-hydroxy-lower alkylammonium salts of (i) to (vii) inclusive; and

(C) Optionally a clarifying agent.

This application is a continuation-in-part of application Ser. No. 464,263, filed May 11, 1965, and now abandoned, saidapplication being a divisional application of applica tion Ser. No. 409,349, filed Nov. 2, 1964, now U.S. Patent 3,391,985, the latter application being in turn a continuation-in-part of application Ser. No. 333,261, filed Dec. 23, 1963, and now abandoned.

This invention, in a first aspect, relates to a process for the continuous pad-dyeing of natural and synthetic polyamide and other textile fibers, as well as pad liquor and novel carriers suitable for use in this process.

It is known that polyamide fibers can be pad-dyed by continuous processes. A known process of this type comprises impregnating wool with an aqueous, thickened solution of acid wool dyestuffs (pad liquor) at temperatures below the drawing temperature of these dyestuffs, then drying the goods and fixing the dyestuff by passing the goods through a hot acid bath (so-called acid shock) and rinsing. As this process has proved to have serious disadvantages, for instance, by producing uneven dyeings, it has not gained practical importance.

As a further development of this process, it has already been suggested to add carriers to the impregnation liquor. As such, the condensation products of fatty acids having 8 to 14 carbon atoms or mixtures of such acids and 2 equivalents of dialkanolamine have proved to be the best. Such condensation products are obtained by the process described in US. Patent 2,089,212.

However, the use of these improved impregnating liquors still has a number of drawbacks, a main one being that they are not stable. After a few hours, without any apparent exterior cause, they often separate irreversibly into two phases, one poor in auxiliaries and the other rich therein, the latter containing the main amount of dyestulf. This phase formation in the impergnating liquor makes the uniform dyeing, particularly of large batches, more difficult. In order to prevent phase separation in the dye liquor it is necessary to calculate carefully the ratio of dyestulf, electrolyte and auxiliaries to each other which makes the constancy of performance of the process considerably more difiicult and adversely aifects its effective range of application.

In order to prevent this undesirable phase separation in the dye liquor, it has also been proposed to introduce into the liquor used for padding wool and the like polyamides soluble salts of saturated aliphatic monocarboxylic acids having 8 to 14 carbon atoms, or polyglycol ethers of alkanols or fatty acids having 8 to 14 carbon atoms, and having 4 to 12 ether groups, or by using the condensation products of fatty acids and dialkanolamine mentioned above according to US. Patent 2,089,212 together with non-foaming, anion-active dispersing agents such as tetrahydronapthalene sulfonic acid. However, the stable pad-liquors thus obtained require a pH above 5.0 and preferably a neutral to alkaline pH range in order to remain homogeneous. This is disadvantageous for the dyeing of polyamide fibers and particularly of wool and undesirable because it excludes the use of certain commercially valuable wool dyestuffs which require after-chroming in a pH range below 5.0 such as Eriochrome Black dyestuffs.

It is, therefore, the main object of this invention to provide a continuous process for the pad-dyeing of natural polyamide fibers, especially wool or synthetic polyamide fibers, in a wide pH range embracing also acid pH Values at low as 2.

The process according to the invention comprises:

(I) Impregnating the said polyamide fibers with an aqueous pad-liquor which contains, as essential constituents, an amount of to 100 grams, and preferably 20 to 40 grams, per liter of liquor, of a dyestuif carrier according to the invention as defined in detail below; noncationic dyestuff capable of drawing on the above-listed fibers from a pad liquor of a pH ranging from 2 to and, optionally, as a clarifying agent, a lower alkanol, of preferably 3 to 4 carbon atoms, especially isopropanol or a fi-alkoxy-ethanol of a total of from 3 to 8 carbon atoms, such as fi-methoxyethanol, ,B-ethoxyethanol or fl-hexoxyethanol, or mixtures of isopropanol and the aforesaid alkoxy-ethanols; said impregnation being carried out at a temperature below the drawing temperature of the respective dyestuffs being used and at a pH of about 2 to 10, and

(II) Fixing the dyestuif in the treated goods by a heat treatment in a humid medium, preferably without intermediate drying, by treating the goods with hot steam and/ or passing them through a hot acid bath.

According to a first aspect of the invention, the abovementioned dyestuff carrier, upon the composition of which the successful dyeing according to the invention depends, consists essentially of a mixture of (A) An unsulfated amide or a mixture of unsulfated amides of a substantially saturated aliphatic monocarboxylic, i.e. fatty acid from 10 to 14 carbon atoms in the lipophilic radical, or of a lower alkanoic acid which is substituted by higher alkylphenoxy wherein the higher alkyl moiety has from 8 to 12 and preferably 9 carbon atoms; or of a mixture of such fatty acids which mixture of acids has preferably an average number of more than 10, and preferably 12 to 16 carbon atoms, amidified with primary or secondary amines containing at least one hydroxy-lower alkyl group which may be etherified.

More specifically, unsulfonated amides defined under (A) supra, which can be used in the pad liquors according to the invention are desired from, for example, caprylic, pelargonic, capric, lauric or myristic acid, or, preferably, from the acid mixture of fatty acids obtained from coconut oil, or from lower fatty acids substituted by alkylphenoxy radicals, in particular alkylphenoxy-acetic acids, wherein the alkyl moiety has from 8 to 12 and preferably 9 carbon atoms, e.g. octylor nonyl-phenoxyacetic acid, and the following aliphatic amines:

(a) Mono-hydroxy and di-hydroxy-mono-alkylamines such as B-hydroXyethyl-amine, 'y-hydroxypropylamine, 8, dihdroxy-mono-propylamine;

(b) Bis-(hydroxyalkyl)amines preferably of a total of from 4 to 6 carbon atoms such as bis-(fi-hydroxyethyly amine, bis-('y-hydroxypropyl)-amine, bis-,(a-methyl-B-hw droxyethyl) -amine;

(c) N-lower alkyl-N-(hydroxyalkyl)-amines, preferably N-methyl-N-w-hydroxyalkylamines, wherein the hydroxyalkyl group has from 2 to 3 carbon atoms, or the corresponding N-ethyl-substituted amines, e.g. N-methylor N-ethyl-N-(B-hydroxy-ethyl)-arnine, or N-methylor N-ethyl-N- 'y-hydroxypropyl) -amine;

(d) Amino-lower alkyl ethers, especially mono-(walkoxy-alkylyamines of a total of from 3 to 5 carbon atoms, at least two of which pertain to the alkyl moiety, such as fi-methoxyor ,B-ethoxy-ethylamine or 'y-methoxyor 'y-ethoxy-propylamine.

(B) (1) Sulfated alkanols of from 8 to 14 carbon atoms; or (2) sulfated, surface-active organic polyglycol ether or a soluble salt thereof, which polyglycol ether is the condensation product of an alkanol or a higher alkyl phenol with ethylene oxide or propylene oxide in molar ratios rangingfrom 1 to 20, the terminal hydroxy group of which condensation product has been sulfated, such sulfated polyglycol ether being more in particular a :sulfated condensation product of an alkanol of 8 to 14 Carbon atoms, with ethylene oxide condensed with each other in a molar ratio of from 1:1 to 1:20, and preferably from 1:2 to 1:5; or a sulfated condensation product of alkylphenol, the alkyl moiety of which has from 8 to 12 carbon atoms, with ethylene oxide, in a molar ratio of from 1:1 to 1:20, and preferably 1:2 to 1:3, e.g. sulfated glycol ethers of octyl-phenol or nonylphenol; or, preferably an alkali metal, ammonium, lower alkylammonium or w-hydroxy-lower alkylammonium salt of (1) or (2).

The ratio of acid amides (A) to the Sulfated alkanols or polyglycol ethers (B) ranges from about 5:1 to 1:5, preferably 2:1 to 1:2, and optimally 3:2 to 121.5, and, when the above-mentioned clarifying agent is present in order to ensure homogeneity of the carrier mixture for a period of several months and even a year or more, the proportions by weight of (A) to (B) may range from about 2:1 to 1:2, and preferably 3:2 to 1:15, and the content of said clarifying agent ranges from 4 to 20% by weight, calculated on the total weight of said mixture.

Of course, the pad liquors according to this aspect of the invention can also be prepared, shortly prior to use, from the individual constituents (A) and (B) of the above-described carrier mixture in the proportions given, in which case the addition of a clarifying agent is superfluous. In this case, the amide (A) is heated to render the same readily flowing and is added with stirring to an aqueous solution of the constituent (B).

The addition of clarifying agent hereinafter referred to as component (C) assists fiowability of the carrier mixture, but does not affect the collor depth of the dyeing obtained in the process according to the invention.

The combination of the components (A) and (B) defined above is highly satisfactory both with regard to the stability over a wide pH range of the dye liquors prepared therewith, even when this is done without use of thickener.

The color yield and fastness properties of dyeings achieved therewith, especially on wool, are unexpected, since the unsulfated amide component (A) used alone as carrier does not lead to stable aqueous solutions at neutral and higher pH but, on the contrary has a tendency to separate out more or less rapidly, forming an upper layer on the dyebath. Moreover, dyeings obtained with such amide component often yield dyeings on wool which are of inferior wash fastness, especially fastness to alkaline milling, as compared with dyeings obtained under otherwise identical conditions with the mixed carriers according to the invention.

On the other hand the sulfated polyglycol ether component, used alone as carrier suffers from the drawback, also shown by the unsulfated polyglycol ether, of causing pronounced sandwich effects, e.g. on wool dyeings produced therewith. Such sandwich effects are particularly disturbing on black dyeings, but also on blue, red or green dyeings, and are only less noticeable on yellow or orange dyeings, thus seriously limiting the field of applicability of such compounds as sole carriers. This becomes particularly noticeable when such dyeings are steam-fixed on modern continuous steaming apparatures. Also the blowing effect on wool slubbings and the like materials imparting fluffiness thereto, is not as satisfactory with unsulfated amides used as sole carrier, in lieu of the mixed carriers according to the invention. The importance of this effect will be explained further below.

In the dyestuif liquors according to the invention, especially. when pronouncedly acid in nature, and particularly in the pad liquors obtained therewith which have a strongly acid pH of 2 to 5, the sulfates (B) are usually saponi'fied so that the respectively substituted free sulfuric acids are present therein.

The above-described, sulfated, surface-active polyglycol ethers used in preparing the carrier mixture according to the invention are produced in a conventional manner by first condensing a suitable alkanol or alkylphenol falling under the definition given hereinbefore, with the corrseponding number of ethylene oxide moles in the presence of a suitable alkaline catalyst such as sodium ethylate or caustic soda, and subsequent sulfation with chloro sulfonic acid and, finally, neutralization with a suitable cation donor to form the desired salts of the respective sulfated polyglycol ether. Details of the method for producing these compounds are to be found in British Patent 463,624, granted to I. G. Farbenindustrie in 1937, and elsewhere.

Lower when used in this specification in connection 'with an aliphatic radical means that such radical has from 1 to maximally 4 carbon atoms.

According to a second aspect of the invention, the above-mentioned dyestutf carrier, the composition of which is an important and critical feature in the process of the invention, consists essentially of a mixture of An unsulfonated amide as defined under (A), supra, and

(CC) a sulfated N-hydroxy-lower alkyl substituted amide of analiphatic mono-carboxylic acid, which is optionally substituted and has at least one lipophilic radical, which amide is obtained by condensation of the acid with primary or secondary amines having at least one hydroxylower alkyl group, and more particularly, (a) sulfated substantially wholly saturated fatty acid monoor di-(B- hydroxyethyl)-amides the fatty acid radicals of which have 8 to 14, preferably about 12 carbon atoms (including the COOH group), in particular sulfated coconut oil fatty acid mono-,8-hydroxyethyl-amide; or (b) sulfated (higher alkylphenoxy)-substituted lower alkanoic acid amides N-substituted as described above, in particular alkylphenoxy acetic acid mono-B-hydroxyethyl-amides and, preferably, alkylphenoxy acetic acid bis-,B-hydroxyethyl amides, the higher alkyl radical of which substituted at the phenoxy moiety has 8 to 12, preferably 9 carbon atoms, for example, sulfated nonylphenoxy acetic acid bis-fl-hydroxyethyl amide; or (c) sulfated hydroxy-substituted unsaturated fatty acids and the lower alkyl esters -of these acids, the acyl radiacl of the fatty acid having from 15 to 18 carbon atoms, preferably sulfated ricinoleic acid, sulfated butyl ricinoleate or mixture thereof obtained by sulfating castor oil (Turkish red oil).

The weight ratio of the sulfated compounds to the nonsulfated compounds being in the range of :1 to 1:5, and preferably from 2:1 to 1:2.

The admixture of such a carrier mixture according to the second aspect of this invention to an aqueous dyestuff solution or pad liquor allows continuous padding, in particular in the pH-range of 7 to 2.

The sulfated compounds defined under (CC) are usually employed in the form of their soluble salts, in particular their alkali, ammonium, lower alkyl or hydroxyalkyl-ammonium salts, in the latter case the dior tri- (B-hydroxyethyl-amine)-salts.

The same stabilizing agents improving the homogeneity and storability of pad liquors as used according to the first aspect of the invention can also be used in the second and all subsequently described aspects of the invention in the same proportions as given hereinbefore.

That the combination of the components (A) and (CC) defined above is highly effective as dye carrier over a wide pH range of the dye liquor in which they are applied and leads to very satisfactory results, is especially surprising since the unsulfated amide component (A) used alone does not lead to stable aqueous dye solutions of neutral or higher pH but, on the contrary, separates out rapidly, forming an upper layer; on the other hand, the sulfated component (CC) when used alone as a carrier under otherwise identical conditions as component (A) yields dyeings especially on wool which lack in wash fastnesses, in particular in fastness to alkaline milling.

Similarly satisfactory dyeings are obtained with carriers which are well suited in the process according to the invention and comprise, as first component, an unsulfated amide as defined under (A), and, as second component, a

mixture of the sulfated compounds defined under (B) and (CC), in which mixture the ratio of (B) (CC) is preferably in the range of 5:1 to 1:5, an optimally in the range of 2:1 to 1:2.

According to a third aspect of the invention, the abovementioned dyestuff carrier consists essentially of An unsulfated amide as defined under (A) supra, and

(D) A sulfated (alkylphenyl)-(2,3-dihydroxypropyl)- ether the alkyl radical of which has 8 to 12, preferably 9 carbon atoms or a mixture of the sulfated amide men tioned under (CC) with a sulfated ether as defined under (D) or of the soluble salts of these sulfated compounds, respectively, in the proportions given under the second aspect of the invention.

What has been stated hereinbefore with regard to the proportions of carrier components and operating conditions, stabilization of pad liquors, etc. under the second aspect of the invention applies equally to this third aspect.

Sulfated (alkylphenyl) (2,3-dihydroxypropyl) ethers usable according to the invention are primarily sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether.

Such ethers are obtained by the reaction of glycol chlorohydrin or 1-chloro-2,S-dihydroxy-propane with the corresponding alkylphenols and sulfating the resulting dihydroxy compounds by methods known er se.

Organic fibers which are dyed according to the invention are, among others, polyester fibers such as cellulose dito tri-acetate, especially, however, also high-molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, e.g. polyterephthalic acid glycol esters, or polyurethans, as well as, polyolefine, especially polypropylene, chiefly, however, synthetic and natural polyamide fibers such as nylon, wool or silk.

The capability of the dyestuffs, used in the process of the invention, of drawing on the goods made from the aforesaid fibers can be readily determined by simple routine tests, with which any dyer is familiar.

The process of the invention yields uniform dyeings also with material of great yardage.

The drawing temperature of the dyestuffs used, i.e. the temperature at which the dyestuff draws within about a minute upon the fiber, is usually about 70 C. or more. Impregnating according to the invention has to be effected below this drawing temperature.

Non-cationic dyestuffs capable of drawing on fibers falling under the above-described group under the conditions given, are mono-azo and poly-azo, preferably disazo, dyestuffs, namely metal-free, metallizable and heavymetal-containing, in particularly chromium-, cobalt-, nickeland copper-complex azo dyes which comprise also the formazane dyes, furthermore, anthraquinone, nitro and methine dyes, acid triphenylmethane and xanthone dyes, naphthazarine dyes and quinophthalone dyes, and also copper phthalocyanine dyes.

To these dyestuffs, there pertain, on the one hand, dyestuffs which are soluble in neutral, acid, or basic medium, within the pH range specified above, and, on the other hand, dyestuffs which are dispersible in water.

Finally, in addition to or instead of dyestutf, the impregnating liquor according to the invention can also contain bactericidal and fungicidal compounds as well as agents which protect against insects, i.e. moth-proofing agents such as the compounds of the formula and which are of the type of known commercial products such as Mitin and Eulan.

As far as the various above-listed textile fibers are concerned, suitable dyestuffs for natural and synthetic polyamide fibers are the so-called acid wool dyes which comprise the above-listed azo, anthraquinone, triphenylmethane and xanthone dyes, and, in particular, also those con taining fiber-reactive groups, i.e. so-called reactive wool and cotton dyes, derived from azo, anthraquinone or phthalocyanine dyes.

For these fibers, and, chiefly for W001, the water-soluble so-called acid wool dyestuffs, particularly also heavy metal-containing, i.e. chromium-, cobaltor copper-containing, azo dyestuffs, including formazane dyestuffs, especially metallized monoazo dyestuffs which contain one metal atom to two molecules of azo dyestuffs are preferred. Chrome dyestuffs are also suitable for these fibers, particularly chromable azo dyestuffs, which latter are used with chromium (III) salts or soluble chromates, preferably in acid medium. When acid dyestuffs are used for dyeing polypropylene, the latter should be of the basically modified type.

For polyester, and polyolefine, in particular polypropylene fibers, there are suitable for use according to the invention azo, anthraquinone, nitro and methine dyestuffs free from water-solubilizing groups, naphthazarine and quinophthalone dyes, while polyurethane fibers as well as synthetic polyamide fibers such as the various types of nylon can be dyed satisfactorily with the aforesaid watersoluble dyestuffs, and also with disperse dyes of the group listed above.

As thickeners, those products which are conventional in textile printing are used, e.g. carob bean flour, galactomannan, tragacanth, dextrin, British gum orin alkaline -mediumalso the water-soluble salts of alginic acid. Cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose can also be used.

The thickeners must not cause the formation of precipitates in the pad liquor under the conditions of the abovedescribed dyeing method, i.e. they should be acid-resistant.

Insofar as suitable apparatus is available, the organic fibers to be dyed according to the invention can be in any from desired. For example, they can be in the form of flocks, slubbing, yarn or fabrics. Such forms of the fibers can be treated on the apparatus shown in the accompanying drawing which is described in detail in Belgian Patent No. 641,637, granted June 20, 1964 to Ilma S.A. Schio, Italy. The material to be dyed can also be in the form of mixed fibers which can consist, for example, of polyamide fibers and cellulose fibers, or in the form of blended fabrics, particularly from wool and polyester fibers such as cellulose acetate, cellulose triacetate and, particularly, polyterephthalic acid glycol ester fibers. In these mix tures, only the polyamide (e.g. the wool) or also the polyamide and polyester components can be dyed simultaneously with dyestuffs suitable therefor.

The fibers are impregnated, for example, by printing, in which case wool can be previously chlorinated, as is conventionally the case prior to printing thereon, or the fibers can be impregnated by coating or spraying, preferably, however, by padding (foularding). The impregnating solution (pad liquor) according to the invention is advantageously prepared by mixing warm aqueous dyestuff solutions or dispersions of suitable concentration, which contain thickeners, with the desired amount of carrier mixture according to the invention, as defined hereinbefore, as well as, optionally, other additives. The polyamide fibers are impregnated advantageously at to 70 C. and then squeezed out to the desired content of impregnating liquor which is about to 130%, and preferably to 100%, of the weight of the fiber (400 grams to 1,300 grams per kilogram of goods).

The impregnated fibers are then steamed by the usual methods, advantageously with neutral saturated steam.

Subsequent to the aforesaid steaming, the dyestuff is preferably fixed on the fibers by treatment in a hot acid bath by known methods (acid shock). The acid content is advantageously about 9 to 10 grams per liter. Preferably, the goods are introduced into the acid bath at to 98 C. To adjust the acid pH value of the bath, inorganic and organic acids are suitable, e.g. sulfuric, phosphoric or hydrochloric acid or formic or acetic acid. Organic acids are preferred, in particular formic acid. In some cases it is useful to add watersoluble salts, preferably water-soluble calcium salts to the acid bath. Development can also be performed by continued steaming as well as, in the'case of polyamide fibers, with hot dilute acid.

The fixed goods are then advantageously rinsed, e.g. with cold or warm Water which can contain the auxiliaries usual in the dyeing industry, e.g. formic acid or acetic acid or also wetting or detergent substances.

Pad liquors suitable for carrying out the padding process according to the invention can also be prepared from pre-mixed pastes which contain as the essential ingredients: (a) 8 to 35%, and preferably 10 to 20% by weight of a suitable dyestuff as defined hereinbefore; (b) 5 to 25% by weight of a dyestuff carrier mixture according to this invention, the aforesaid percentages being calculated on the total weight of the paste; the balance consisting of (c) water; and, furthermore, optionally, ((1) depending on the nature of the dyestuff; acid or alkaline agents such as, in particular, acetic acid, formic acid, sulfuric acid, phosphoric acid, sodium or potassium carbonate or bicarbonate, sodium or potassium acetate, or sodium or potassium hydroxide, in amounts sufiicient to adjust the pH of the paste to a value most compatible with the dyestuff and with the maintenance of a satisfactory homogeneity of the paste; and, optionally of, (e) thickener in sufficient amount to impart to the paste a viscosity in the range of from 1 to 50, and preferably 10 to 40, poises.

A homogeneity-enhancing agent such as isopropanol or one of the other compounds mentioned hereinbefore for the carriers according to the invention, is especially present in the paste in those cases Where the latter is prepared from carriers according to the invention listed above.

Pad liquors for use in the method according to the invention are prepared from these pastes by diluting the latter with water, preferably in such proportions that 1 kg. of pad liquor is obtained from every 100 to 400 g. of paste, depending on the desired depth of shade of the resulting dyeings.

The use of such pastes in the preparation of pad liquors represents a considerable advantage over the conventional preparation from the individual constituents, and, usually, the dyestuffs are present in the pad liquors thus prepared from pastes according to the invention, in a fine and particularly uniform distribution, especially independent of the amount of pad liquor being prepared, which is not easily achieved and not as easily reproducible by preparation of the pad liquors by other methods.

The process according to the invention for the dyeing of organic fibers has remarkable advantages over similar known processes. The main advantage consists in the pH range which stretches very far and deep into the acid reigon at which dyeing can be performed, so that the most favorable dyeing conditions can be chosen Without the pH of the liquor being taken into consideration. Thus, for example, because of the possibility of dyeing in the acid range also, certain chromable dyestufis such as Eriochrome Black T can be used with chromium (III) salts. This has not been possible previously.

Another advantage of the process according to the invention is that the pad liquors are homogeneous under the conditions of the above-described dyeing method and remain so for a long time, as mentioned hereinbefore.

While known pad liquors, especially those consisting of two phase emulsions, which form a so-called coacervate easily suffer phase separation within a relatively short time, require special adjuvants such as alglnates to postpone this separation, and, once such separation has occurred, yield spotty, unlevel dyeings, the pad liquors according to the invention need no such stabilizing adjuvants and remain stable since they are one-phase systems.

They thus do not require such careful adjustment of the proportions of the ingredients, are simpler to prepare, and do not require special stabilizing adjuvants but can be used with satisfactory results, after standing for weeks or even months.

Dyeings obtained with the pad liquors according to the invention show good dyestutf yields due to particularly good fixability of the dyestoff on the fibers after padding, without any special further adjuvants. In particular, dyed fibers and filaments padded according to the process of the invention are, to our knowledge, the first that permit successful fixation of the fiber by steaming directly following padding. For instance, when steaming fibers or slubbing, these goods are given a fluffy texture blowing up the space occupied by the padded goods by just the right amount, namely about 1 /2 to three times the original volume, but not further so that no entanglement of the fibers occurs which might disturb passage of the material through the steaming apparatus, whereby a rapidly fixable material is obtained. The desirable blow-up of the texture practically never occurs if the mixed carriers according to the invention in the pad liquors used in the abovedescribed process are replaced by the individual components of these mixed carriers, e.g. the sulfated polyglycol ether alone, or the fatty acid amide component alone. Some known mixed carriers, on the other hand, lead to excessive blow-up, disorientation of the fibers in the material and the abovementioned disturbances in the steaming operation.

Use of either component alone, in lieu of the highly critical mixtures of the two components as defined above also leads to other drawbacks, such as dependence on, for instance, wool of specific origin, while wool blends from different origin can be dyed evenly in the same bath with the pad liquors according to the invention. Another drawback of pad liquors containing as carriers only one of the two components of the mixed carrier according to the invention, is the formation, during fixation by steaming, of the so-called sandwich effect mentioned hereinbefore, which imparts a greyish hue to the finished dyeings.

As a further advantage, dyeing with pad liquors according to the invention permits much shorter steaming times, for instance, depending on the nature and concentration of the dyestuffs, only 20 minutes, where, with the same dyestuif in the same concentration, use of a known carrier would require 40 minutes of steaming, or more.

Moreover, the dyeings obtained e.g. on wool or other fibers by continuous dyeing processes as outlined above using in the dye liquors the carrier mixtures according to the invention show improved wet fastness properties especially wash fastness such as fastness to alkaline milling, compared with dyeings similarly prepared, but with the aid of known carriers in lieu of those according to the invention.

Carrier as used in this specification and the appended claims means a color transfer agent which assists in carrying the dyestuff from a pad liquor or paste on and into the fiber to be printed.

The following non-limitative examples serve to illustrate the invention further. The temperatures given therein are in degrees centigrade. Where not otherwise stated, parts and percentages are given by weight. The relationship of parts by weight to parts by volume is as that of grams (g.) to milliliters (ml.).

10 EXAMPLE 1 40 parts of the commercial form of the chromium complex compound of the monoazo dyestuff Z-aminophenol- 4-methylsulfone 1-phenyl-3-methyl pyrazolone (molar ratio of dyestuff2chromium is 2:l)containing about 50% of dextrin as diluting agentare dissolved in a 60- warm mixture of 300 parts of an aqueous 2.5%-solution of carob bean flour and 30 parts of a carrier mixture consisting of the sodium salt of sulfated lauryl alcohol diglycol ether [C H (OC H OSO Na], coconut oil fatty acid N,N-bis-(B-hydroxyethyl)-amide and isopropanol in a weight ratio of 9:9:2, and 250 parts of water. The resulting solution is diluted to 900 parts with warm water (60 C.) and the pH is adjusted to about 2.5 with formic acid. The temperature of the mixture should then be about 50. This solution is then diluted with water to 1000 parts. Wool flannel is impregnated at 50 with this liquor, squeezed out to a liquor content of about 100% calculated on the dry weight of the fibers and steamed with saturated steam for 15 minutes at 98. The goods are then washed first with a solution containing 1 gram (g.) per liter of nonylphenol-polyglycol ether condensation product (molar ratio about 1:12), then rinsed with water and then washed with an aqueous solution containing 2 milliliters (ml.), per liter, of formic acid and again rinsed with water.

A level, well penetrated orange wool dyeing is obtained which has no so-called sandwich effect.

By using in the above example, instead of the dyestuff mentioned, similar chromium-containing monoazo dyestuffs of the type containing 2 dyestuff molecules per chromium atom (2:1 complexes) which contain no sulfonic acid groups but which are substituted by lower alkyl-sulfonyl groups or which contain sulfonic acid amide groups which may be substituted at the nitrogen atom by alkyl groups, for example, the chromium-containing dyestuff: Z-aminophenol-S-sulfonic acid amide- 1-phenyl-3-methyl-pyrazolone; the chromium-containing dyestutf mixture: 2-amino 5 nitrophenol-e 2-h-ydroxynaphthalene, 2-amino-5-nitrophenoll-hydroxynaphthalene3,6-bis-sulfonic acid methylamide (dyestuff2chromium=2:l); or the chromium-containing monoazo dyestuff: 2 aminophenol 4 methylsulfoneacetylamino-7-hydroxy-naphthalene (dyestulf chromium=2: 1), while otherwise the procedure given in the above example is followed, equally well penetrated and level red, navy blue or grey colored wool flannel dyeings, respectively, are obtained.

By using, instead of the carrier mixture given in the above Example 1, 20 parts of a carrier mixture prepared by mixing with each other: 9 parts of the ammonium salt of sulfated lauryl alcohol triglycol ether 9 parts of coconut oil fatty acid-N,N-bis-(hydroxyethyl)- amide, and 2 parts of isopropanol, and following the procedure given in the example, paragraph one, equally well penetrated and level dyeings are obtained.

Also diand tri-ethanolamine salts of sulfated lauryl-triglycol ether can be used instead of the ammonium salt.

EXAMPLE 2 Woolen slubbing is padded with the liquor described in the first part of Example 1, the pH of which, however, has been adjusted to 4 with acetic acid instead of formic acid, and the procedure given in the first part of Example 1 is followed, and the four dyestuffs employed in Example 1 are used, respectively.

'Equally well penetrated and level orange, red, navy blue or grey dyed woolen slubbing is obtained.

Turquoise dyeings of similarly good qualities are obtained by repeating Example 2, but using, instead of the 11 I 40 parts of dyestuff used therein, 20 parts of the dyestufI of the formula EXAMPLE 3 By repeating the above Example 2, but using, instead of the dyestuffs, employed therein 20 g. of the copper complex of the dyestuff of the formula produced as described in Example 2 of the US. Patent 2,839,521 to Schetty, issued June 17, 1958, wool slubbings of very fast, light brown shades are obtained.

EXAMPLE 4 By repeating the above Example 2, but using, instead of the last-mentioned dyestutf, 18 g. of the dyestuif of the formula 1 Hogs SO3H wool slubbings of particularly brilliant red shades are obtained.

EXAMPLE 5 W001 flannel is impregnated at 60 with pad liquor prepared as described in the first part of Example 1 and squeezed out to a liquor content of about 100%. The foularded fabric is introduced into a 9 8-warm aqueous bath which contains 8 mL/liter of 85% formic acid, and is left in this bath for 5 minutes. The wool flannel so dyed is then washed with a 45-warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether for 5 minutes, whereupon it is rinsed with cold water. The resulting orange dyeing is well penetrated and has no sandwich effect.

By using, instead of the carrier mixture used in Example 1, 40 parts of a mixture consisting of 24 parts of the potassium salt of sulfated myristyl alcohol pentaglycol ether [C 'H (OC H OSO K], 12 parts of coconut oil fatty acid N,N-bis-(hydroxyethyl)-amide, and 4 parts isopropanol, and following the procedure, other wise, as given in the example, then equally well penetrated and level dyeings are obtained.

Instead of the potassium salt of sulfated myristyl alcohol pentaglycol ether, also the potassium or sodium salt of sulfated octylphenol diglycol ether can be used.

EXAMPLE 6 (a) Woollen slubbing is impregnated at 40 on a pad mangle with an impregnating liquor which contains the dyestuff of the formula SO Na instead of the azo dyestuff mentioned in the first part of Example 1 and which is otherwise prepared as described in Example 1. The slubbing is squeezed out to 100% content. The goods are then steamed under for 15 minutes at 98.

They are then Washed first with a solution containing 1 g. per liter of nonylphenol polyglycol ether, then rinsed with water, then washed with an aqueous solution con taining 2 ml. per liter of aqueous %-formic acid and, optionally, rinsed with water.

A level and well-penetrated red woollen slubbing is obtained which has no sandwich effect.

By using, instead of the aforesaid dyestuif (b) the disazo dyestuif coupling in an acid medium according to the formula NH2 S Cl 3 l S 0 11 NH2 or (c) the chromium-containing (chromium to dyestuif ratio 1:2) dyestuff obtained from the metallizable azo dyestuff of the formula and otherwise following the procedure given in the above example then equally well penetrated and level red or yellow colored material, respectively, is obtained.

EXAMPLE 7 5 parts of the black dyestuif of the formula duced by mixing with each other 13.5 parts of the sodium salt of sulfated lauryl alcohol diglycol ether 13.5 parts of coconut oil fatty acid N,N-bis-(p-hydroxyethyl)amide, 1.5 parts of fi-methoxy-ethanol, and 1.5 parts of isopropanol, which 30 parts have been dissolved in 500 parts of warm water, are added to the solution.

A mixture consisting of: 20 parts of chromium fluoride (CrF and 50 parts of an aqueous 20%-solution of chromium acetate which has been previously boiled is added to the solution obtained, the resulting solution is brought to 900 parts with warm water and 20 m1. of aqueous 85%-formic acid are added to the solution which is then made up to 1000 ml. with water. The temperature of the ready solution should be about 50.

Woollen slubbing is impregnated at 50 with this liquor, squeezed out to a liquor content of about 100% and steamed with saturated steam for 30 minutes at 98.

The slubbing is then rinsed in a first bath in a backwashing machine at 40 and then treated for 15 to 30 seconds in a second back-washing machine 'bath in an aqueous solution containing 10 g./liter of sodium bichromate, and 8 ml./liter of aqueous 85%-for-mic acid, at a temperature of 70.

The slubbing is then rinsed in further back-washing machine baths with water of about 40.

Slubbing dyed even black is obtained which can be readily combed and spun.

EXAMPLE 8 Silk serge is imprgnated at 40 with an impregnating liquor produced according to the first part of Example 1, squeezed out to a liquor content of 80% and introduced into a 98 warm aqueous bath which contains 8 ml./liter of 85%-formic acid. It is kept in this bath for 5 minutes. The grained silk is then washed with a 45- warm aqueous solution of 0.5 g./liter of nonylphenol olyglycol ether and then rinsed with cold water.

In this way, a well-penetrated orange-colored silk serge is obtained which is very level without a sandwich effect.

Corresponding yellow dyeings on silk serge of equally good penetration and evenness are obtained if, in the above example, instead of the dyestuff mentioned, the dyestulf used under (c) in Example 6 is used and the procedure given in the example is followed.

EXAMPLE 9 37.5 parts of the chromium-montaining monoazo dyestuff 2-carboxy-1-aminobenzene l-phenyl 3 methylpyrazolone (dyestuffzchromium is 2:1) and 14.0 parts of the chromium-containing monoazo dyestuff Z-aminophenol 4 sulfonic acid methylamide l-carbethoxyamino-7-hydroxynaphtha ene (dyestufi:chromium=2: 1) are dissolved in an 80-warm mixture of 200 parts of an aqueous 2.5%-sodium alginate solution and 10 parts of a mixture of the ammonium salt of sulfated nonylphenol triglycol ether lauric acid N,N-bis-(hydroxyethyl)-amide, and isopropa- 1101, in a weight ratio of 9:18:3 as well as 270 parts of water. The solution is adjusted to pH 8 and diluted with cold water to 1000 parts. The temperature should be about 40 Plain-woven nylon fabric is padded with this liquor, squeezed out to a liquor content of 50% calculated on the weight of the goods, steamed for 8 minutes at a temperature of 130 and then rinsed first with hot and then with cold water.

An olive, well-penetrated, very level nylon dyeing is obtained.

14 EXAMPLE 10 Plain-woven nylon fabric is impregnated at 40 with an impregnating liquor produced according to the first paragraph of Examp e 9 which only contains, however, two thirds of the amount of dyestulf given in that example. The fabric is then squeezed out to a liquor content of 50% calculated on the weight of the fibers, introduced into a 98-warm aqueous bath containing 4 ml. per liter of aqueous 85 %-formic acid and treated in this bath for 4 minutes. The fabric is then rinsed first with warm and then cold water; it is well and evenly dyed olive.

EXAMPLE 11 A plain-woven fabric made from poly-e-aminocaprolactam (nylon 6) is padded at 40 with an impregnating liquor produced according to Example 8. The fabric is squeezed out to a liquor content of 50% ca culated on the weight of the fibers and then dried under thermofixing conditions for 45 seconds at 190.

The Perlon fabric thus treated is introduced into a 98-Warm aqueous bath which contains 4 ml. per liter of aqueous 85 %-formic acid, and is boiled in this bath for 4 minutes. It is then rinsed with warm and cold water.

An olive Perlon dyeing is obtained which is level and Well-penetrated.

EXAMPLE 12 2.5 parts of the cobalt-containing monoazo dyestuff: Z-aminophenol 4-sulfonic acid methylamide l-phenyl- 3-methyl-5-pyrazolone (dyestutf:cobalt=2:1), and 0.5 part of the chromium-containing monoazo dyestuffzZ- amino-4-nitrophenoll-phenyl 3 methyl-S-pyrazolone (dyestuffzchromium=2: 1) are disso ved in an -warm mixture of 300 parts of an aqueous 2.5%-carob beam flour solution and 25 parts of a mixture of: the sodium salt of sulfated laury alcohol diglycol ether, coconut oil fatty acid-N,N bis-(hydroxyethyl)-amide, and B-ethoxyethanol, the weight ratio of the three components being 9:9:2.

The solution is adjusted to a pH of 4 with aqueous 80%-acetic acid, and di uted up to 1000 parts. Woollen slubbing is impregnated at 40 with this liquor, squeezed out to a liquor content of about 100% (calculated on the weight of the fibers) and steamed for 15 minutes at 98 with saturated steam.

The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether and 1 ml./ liter of concentrated ammonia solution, then rinsed with water, washed with aqueous solution containing 2 ml./ liter of aqueous %-formic acid and again rinsed with water.

The orange-yellow slubbing so obtained is well pentrated and very level. The touch of the goods is very loose and voluminous and the material can be readily combed and spun.

EXAMPLE 13 40 parts of the commercial, chromium-containing mon oazo dyestutf 2-aminophenol-4-methylsulfonel-acetylamino 7 hydroxynaphthalene (dyestuif:chromioum= 2:1) and dissolved in a 60-warm mixture of 300 parts of an aqueous 2.5%-sodium alginate solution and 30 parts of a mixture of: sodium salt of sulfated lauryl alcohol diglycol ether, coconut oil fatty acid-N,N-bis-(hydroxyethyl)-amide, and p-hexoxy-ethanol, in a weight ratio of 9:9:2, which mixture is dissolved in 200 parts of water.

The solution obtained is made up to 1000 parts with water. The temperature of the solution should be 60.

Wool flannel is impregnated with this liquor at 60 and squeezed out to a liquor content of about 80%. The padded fabric is introduced into a 98-warm aqueous bath which contains 8 ml./liter of aqueous 8S%-formic acid, and is kept in this bath for minutes.

The grey-colored wool flannel is then washed with a 45 -warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and then rinsed with cold water. A wellpenertated grey wool flannel of level shade Without a sandwich effect is obtained.

By using in the above example, instead of the dyestuff mentioned, the cobalt-containing monoazo dyestutf 2- amino 4 chloro phenol- 2 hydroxynaphthalene 6- sulfonic acid methylamide (dyestutf:cobalt-=2:1) or the chromium-containing monoazo dyestuif 2-amino-4-chlorophenol 1-hydroxynaphthalene-3-sulfonic acid amide (dyestuff:chromium=2:1) and otherwise following the procedure given above in the example, a ruby or blue colored wool flannel, respectively, is obtained. The dyeing is equally well penertated and level.

EXAMPLE 14 40 parts of the commercial form of the dyestuif of the S ogNa are dissolved in a 6 0-warm mixture of 300 parts of an aqueous 2.5%-sodium aliginate solution, 30 parts of a mixture of the ammonium salt of sulfated octylphenolpentaglycol ether,

coconut .oil fatty acid-N,N-bis-(B-hydroxyethyl)-amide, and isopropanol (weight ratio 9:922), which mixture is dissolved in 200 parts of water, as well as 20 parts of ammonium sulfate, and 10 parts of potassium chromate, dissolved in 250 parts of water.

The pH of the resulting solution is adjusted, if necessary, to 7.5 to 8, with acetic acid and brought up to 1000 parts with Water. The temperature should be 50.

Wool flannel is padded with this liquor at 60 and squeezed out to a liquor content of about 100%. The foularded fabric is then steamed with saturated steam for 30 minutes. The resulting blue-colored wool flannel is then washed with a 45 -warm aqueous solution of 0.5 g./ liter of noylphenol polyglycol ether, treated in an acid bath which contains 5 ml./liter of 8'5%-formic acid for to 30 seconds at 70 and then rinsed with 50-warm water. A well-penetrated, very level blue wool flannel is obtained which is free from a sandwich eifect.

By using, in the above example, instead .of the dyestuif mentioned, the dyestuff of the formula NaOOO or the dyestuff of the formula N30 38 O H I rm N=N O\ N (j) C H I and otherwise following the procedure given in the example, correspondingly yellowor red-colored Wool, flannel, respectively, is obtained, The dyeings are equally wellpenetrated ant level.

1 6 EXAMPLE 15 By using, instead of the pad liquors described in Example 14, similar liquors, the pH of which has been adjusted to 3.5 to 4 with aqueous 85%-forrnic acid and which contain, instead of sodium alginate, methyl cellulose and, instead of potassium chromate, 30 parts of chromium fluoride as agent affording chromium, and wool flannel is padded therewith at 50, squeezed out to a liquor take up of about 100 calculated on the weight of the goods and steamed with saturated steam for 30 minutes at 98, then blue, yellow or red-colored wool flannel, respectively, is obtained.

The dyeings have equally good penertation and evenness. If the steaming time is raised from 30 to 45 .or minutes, then dyeings of somewhat more color strength are obtained.

EXAMPLE 16 A fabric consisting of 45 parts of wool and 55 parts of polyglycol terephthalate fiber is impregnated and steamed in accordance with the first part of Example 1. The wool portion is dyed orange while the polyester portion remains practically undyed.

EXAMPLE 17 A mixed fabric of wool and cellulose triacetate (weight ratio 1:1) is impregnated and steamed as described in the first part of Example 1. The wool portion is dyed orange, while the triacetate portion remains practically undyed.

EXAMPLE 18 11 parts of the chromium-containing monoazo dyestuff 2 aminophenol 4 sulfonic acid N,N dimethylamide 1 (3 chlorophenyl) 3 methyl 5 pyrazolone, 1 part of the chromiumcontaining monoazo dyestuff 2 amino-4-methylsulfonyl-benzene carboxylic acid l-phenyl-3-methyl-5-pyrazolone and 0.5 part of the mixed chromium-containing dyestufl 2-amino-4-methyl-sulfonyl-benzene 1 methylsulfonylamino 7 hydroxynaphthalene+1-(4-chlorophenyl)-3-methyl-pyrazolone (the overall molar ration of dyestuffzchromium being 2:1) are dissolved in a 50-warm mixture of 300 parts of an aqueous 2.5 %-carob bean flour solution and 30 parts of a carrier mixture consisting of: di-(B-hydroxyethyl) -amino salt of sulfated nonylphenol triglycol ether,

coconut oil fatty acid-N,N-bis- (hydroxyethyl)-amide, and isopropanol, in a weight ratio of 9:9:2, which mixture has been disoslved in 250 parts of Water.

10 parts of moth-proofing agent of the formula COONa previously dissolved in 100 parts of warm water are I IHSO2-CH2Cl and otherwise following the above-described procedure, a level orange-colored slubbing is obtained which has similar good properties to those described hereinbefore.

EXAMPLE 19 20 parts of the commercial form of the dyestuff of the formula are dissolved in a 60-Warm mixture of 200 parts of an aqueous 2.5%-sodium alginate solution and 35 parts of a carrier mixture consisting of: the tri-(B-hydroxyethyD- ammonium salt of sulfated octylphenol diglycol ether coconut oil fatty acid-N,N-bis-(B-hydroxy-ethyl)-amide, and isopropanol, in a weight ratio of 9:9:2, which carrier has been dissolved in 250 parts of water.

The solution obtained is brought up to about 1000 parts with warm water, whereby the pH should be at about 7 to 8 and, if necessary, this is adjusted with a small amount of acetic acid.

The impregnation liquor thus obtained is used in Example 20 infra.

EXAMPLE 20 Polyethyleneglycol terephthalate slubbing is padded with a liquor produced according to Example 19 at 50 and squeezed out to a liquor content of 60%, calculated on the weight of the goods.

The slubbing is steamed for 30 minutes at 98 with saturated steam, then washed with a solution containing 1 g./ liter of nonylphenol polyglycol ether and rinsed with warm and cold water. A level yellow polyester slubbing is obtained.

If, in the above foulard liquor of Example 19, five parts of p-phenylphenol are added, and otherwise the procedure given in Example 20 is followed, then yellow poly ethyleneglycol terephthalate slubbings of greater color strength are obtained.

EXAMPLE 21 A pad liquor is prepared as described in Example 19 by repeating the same procedure, but using, in lieu of the dyestuff used therein, 20 parts of the dyestuff of the formula This dyestuff is produced as described in Example 1 of patent application Ser. No. 237,755, filed Nov. 14, 1962, but using instead of 17.8 parts of dichloroaniline, an equimolar amount of l-amino-Z-bromo-4-nitrobenzene, and otherwise following the same procedure.

To the resulting pad liquor there are added 5 parts of the sodium salt of o-phenylphenol and 5 parts of diammonium phosphate.

Polyglycol terephthalate yarn is then padded with the resulting liquor and squeezed out to a liquor content of 50% calculated on the weight of the yarn.

The yarn is then steamed for 30 minutes at 98 with saturated steam, then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with warm and cold water. A level greenish-blue polyester yarn is obtained, which is fast to washing and light.

EXAMPLE 22 360 parts of a press cake of the dyestutf of the formula OgN are introduced in batches into a vessel equipped with a turbomixer of the Homo-Rex type manufactured by Broglie & Co., Basel, Switzerland, having a preferred operational speed in the range of about 3,000 to 5,000 rpm, which vessel has been charged with 360 parts of water, and the contents are stirred for one hour at a speed of about 4,000 r.p.m.

In another vessel, a liquor is prepared by mixing 120 parts of a carrier mixture consisting of sodium lauryloxyethoxyethyl sulfate (sodium salt of sulfated lauryl alcohol diglycol ether), coconut oil fatty acid N,N-bis-(B-hydroxyethyl)-amide and isopropanol, in a weight ratio of 919:2, 150 parts of Water, and 10 parts of aqueous %-acetic acid, whereby the pH of the liquor is adjusted to a value below 5.

This liquor is added slowly to the contents of the first vessel while continuing stirring which is terminated 15 minutes after the addition of the liquor from the second vessel is complete.

A completely homogeneous, brown paste ready for use is obtained.

A pad liquor is prepared from 300 parts of the above paste by stirring the same with 350 parts of 60-warm water and parts of an aqueous 2.5%-carob bean flour solution. To the resulting liquor there is added a mixture of 20 parts of chromium trifiuoride and 50 parts of an aqueous 20%-chromium acetate solution which has previously been boiled.

The solution is brought to 900 parts with 60-warm water and 20 ml. of aqueous 85 %-formic acidare added to the solution which is then made up to 1000 ml. with water. The temperature of the pad liquor ready for use is then approximately 50 Woollen slubbing is padded with this liquor in strict accordance with the method described in Example 7, with identically satisfactory results.

EXAMPLE 23 (I) parts of myristic acid N-(v-ethoxypropyD- amide are liquefied by heating and are added slowly to parts of bis-('y-hydroxy-propyl)-ammonium salt of sulfated laurylphenol-hexaglycol ether [bis-('y-hydroxypropyl)-ammonium laurylphenol hexa oxy-ethyl sulfate] in a turbomixer with stirring at about 4,000 r.p.rn., for one hour. The completely homogenized mixture is then dissolved with 2,000 parts of 60-warm water.

19 (II) 20 parts of the dyestutf of the formula (III) Perlon (nylon 6) fabric is impregnated With the pad liquor thus obtained, and then squeezed to leave 60% of liquor, calculated on the weight of the fabric, on the latter. The moist fabric is then directly steamed in saturated steam for 15 minutes.

A blue dyeing of good color depth is obtained.

Similarly good results are obtained when using in the preparation of the pad liquor according to this example, an aqueous 7%-galactomannan (condensation product of the polysaccharides in a molar ratio of about 1:1) solution in lieu of the carob bean solution described above.

Cellulose acetate or triacetate fabrics, or fabrics made of polyvinylalcohol of the Kuralon type (manufactured by Kurashiki Rayon K.K., Japan) or fabrics of polyurethane, of the Lycra-spandex type of fibers (manufactured by E. I. du Pont de Nemours, Wilmington, Del.) are pad-dyed in the same manner as described above for Perlon, and similarly good quality blue dyeing are obtained.

EXAMPLE 24 (I) A carrier mixture according to the invention is prepared in the same manner as described in part (I) of Example 23, but using, instead of 130 parts of the myristic amide and 170 parts of the sulfated laurylphenol hexa-glycol ether salt used therein: 150 parts of capric acid N-ethyl-N- y-hydroxypropyl-amide, and 200 parts of N-methyl-N-y-hydroxy-propylammonium p-octylphenyl-deca-oxyethyl-sulfate, respectively.

(II) 20 parts of the chromium complex dyestutf described in Example 1 of US. Patent No. 2,711,404 are dissolved in hot Water (70) and the solution is slowly added during 5 minutes with stirring to 235 parts of the carrier mixture prepared as described above in part (I) of this example. While continuing to stir, 300 parts of an aqueous 2.5%-carob bean flour solution are added with stirring to the resulting mixture. The liquor thus obtained is diluted with water of about 50 to make up 900 parts, its pH is then adjusted to about 5.5 to 6 by adding an adequate amount of dilute acetic acid, and water is then added to make up 1000 parts of a pad liquor ready for use.

(III) A fabric of polypropylene modified by basic groups, of the Meraklon D type (manufactured by Poly mer Industrie Chimiche, S.p.a., Milan, Italy) is impregnated on the pad with the above-described pad liquor having a temperature of about 50 to 55, and is then squeezed to leave a liquor content of 60 to 70% by weight on the fabric (calculated on the Weight of the fabric prior to impregnation).

The fabric is then steamed for 40 minutes in an atmosphere of saturated steam at 98. The steamed fabric is then Washed in a bath containing 1 gram of nonylp poly-glycol ether per liter of water, and finally rinsed with water, and dried.

A brown dyeing of good color depth and good qualityis obtained.

Similarly, satisfactory brown dyeings are obtained by pad-dyeing a polyurethane fabric (Lycra ty-pe fibers).

EXAMPLE 25 (I) A carrier mixture is prepared as follows: parts of capric acid N-(w-hydroxy-butyl)-amide are liquefied by heating and then added slowly into a turbomixer charged with parts of potassium nonyloxy-(ethoxy) ethyl surfate (potassium salt of sulfated nonyl alcohol decaglycol ether), and the resulting mixture is stirred at 4,000 rpm. for one hour.

Io the resulting, fully homogenized mixture, there are added 20 parts of B-hexoxy-ethanol and 2500 parts of 60-warm water, whereby a clear dyestuff carrier mixture is obtained.

(In) A thickened dyestufl solution is prepared from 218- parts of the above carrier mixture solution and 205 parts of an aqueous solution of 5 parts of the dyestulf used under (c) in Example 6, proceeding in the same manner as described in part (II) of the preceding example.

Similar good yellow dyeings are obtained on the fabrics used in part (III) of Example 24, by proceeding in the same manner as described therein.

Similarly satisfactory results are obtained when using, in lieu of the carob bean flour solution used in Example 24, part (II), the same :amount of an aqueous 2%carboxymethyl cellulose solution.

EXAMPLE 26 Example 25 is repeated, but instead of 8 parts of the capric acid amide used therein, 12 parts of N,N-bis- (fl -hydroxypropyl)-lauramide are used as the first component, and, instead of the 10 parts of the potassium salt of sulfated nonylpolyglycol ether used therein, 14 parts of the potassium salt of sulfated myristyl alcohol tetraglycol ether [C H (OC H OSO K] are used as the second component of the carrier mixture according to the invention, and otherwise following strictly the same procedure as in the preceding example.

This dyestutf carrier solution is employed in parts (II) and (HI) of Example 24 in lieu of the carrier used therein. Similarly good results are obtained.

EXAMPLE 27 (a) 22 g. of the disazo dyestufl? acid 2,2-diamino-4,4-dichloro-diphenyl sulfide 2 2-amino-8-hydroxy-naphthalene-fi-sulfonic acid 6 g. of the dyestuif of the formula SOsH (EH3 CHzNHCO 0112-01 and 13 g. of the chromium-complex of the monoazo dyestuif, 2 amino phenol 4-methyl sulfone 1-phenyl-3- methyl-pyrazolone (molar ratio of dyestutf of chromium=2:1) are pasted with 60 g. of cold water. 750 g. of hot water are added while stirring and the whole is heated to boiling. Then 10 g. of crystal gum thicknening agent are added while stirring. After the thickening agent has formed a clear solution, the solution is cooled to about 50, and 30 g. of acarrier mixture are added which mixture consists of 9 parts of nonylphenoxy-acetic acid bis-,S-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diethyleneglycol ether and 2 parts of isopropanol. 160 g. of an aqueous solution consisting of 40 g. of 85% formic acid and 120 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50; the slubbing is then squeezed on a pad mangle to a liquor content of about 100% calculated on the dry weight of the goods. The slubbing is then steamed for 30 minutes in saturated steam at 100-102. After steaming, the goods are washed with about 40 warm water, and subsequently, at 40, with an aqueous solution containing 1 gram per liter of nonylphenol polyglycol ether. Then it is rinsed and dried. A Bordeaux-colored slubbing is obtained which has no sandwic effect.

Equally good dyeings without a sandwich effect are obtained when the carrier mixture used in the example is replaced by equivalent amounts of one of the following mixtures, the procedure being otherwise the same as described:

(b) 9 parts of nonylphenoxy acetic acid-bis-B-hydroxyethyl amide, 9 parts of the ammonium salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol, or

(c) 9 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide. 9 parts of the di-fi-hydroxyethyl amine salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol, or

(d) 9 parts of nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 9 parts of the tri-B-hydroxyethyl amine salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol, or

(e) 12 parts of dodecylphenoxy acetic acid bis-p-hydroxyethyl amide, 24 parts of the potassium salt of sulfated myristyl alcohol pentaglycol ether and 4 parts of isopropanol, or

(f) 12 parts of noylphenoxy acetic acid bis-B-hydroxyethyl amide, 24 parts of the sodium or potassium salt of sulfated octylphenol digylcol ether and 4 parts of isopropanol, or

(g) 13.5 parts of nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 13.5 parts of the sodium salt of sulfated lauryl alcohol digylcol ether, 1.5 parts of isopropanol and 1.5 parts of fi-methoxy-ethanol, or

'(h) 18 parts of nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 9 parts of the ammonium salt of sulfated nonylphenyl triglycol ether and 3 parts of isopropanol, or

(i) 12 parts of nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, and 14 parts of the potassium salt of sulfated myristyl alcohol tetraglycol ether, or

(k) 15 parts of nonylphenoxy acetic acid-fl-hydroxyethyl amide and parts of the N-methyl-N-(y-hydroxypropyl) amine salt of sulfated octylphenol decaglycol ether, or

(1) 9 parts of octylphenoxy acetic acid bis-B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol, or

(m) 9 parts of nonylphenoxy acetic acid mono-fihydroxyet-hyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol,

(n) 12 parts of nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 12 parts of the potassium salt of sulfated myristyl alcohol pentaglycol ether and 12 parts of the ammonium salt of sulfated nonylphenoxy acetic acid bisfi-hydroxyethyl amide, or

(o) 15 parts of nonylphenoxy acetic acid-,G-hydroxyethyl amide, 10 parts of the N-methyl-N-(v-hydroxypropyl)-amine salt of sulfated octylphenol decaglycol ether and 10 parts of the sodium salt of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, or

(p) 10 parts of nonylphenoxy-acetic acid bis-(fi-hydroxyethyl)-amide and 14 parts of potassium lauryl sulfonate.

EXAMPLE 28 35 g. of the dyestuff 1-amino-6-nitro-2-hydroxy-naphthalene-4-sulfonic acid-a2-hydroxyna-phthalene are pasted with 60 g. of cold water and dissolved in 770 g. of hot water by heating to the boiling temperature. 50 g. of an aqueous acetic acid solution consisting of 10 g. of acetic acid and 40 g. of water are slowly added to this solution. Then, 8 g. of galactomannan thickening agent pasted with a small amount of ethanol for better solubility, are added while stirring. Upon dissolution of the thickening agent, the mixture is cooled to about 50, and 35 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. 20 g. of formic acid as well as a dispersion consisting of 80 g. of water and 40 g. of chromium fluoride are added to this solution.

This pad liquor is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about calculated on the dry weight of the goods. The slubbing is then steamed at 100 to 102 with saturated steam. After steaming 30 minutes, the goods are washed with about 40 warm water and subsequently at 40, with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether; then it is rinsed and dried.

In this manner a black dyeing is obtained which has no sandwich effect.

When the carrier mixture used in the example is replaced by one of the mixtures Nos. (b) to (p) of Example 27 the procedure being otherwise the same as before, a black dyeing is also obtained which is free from a sandwich effect.

Similar satisfactory results are achieved by carrying out the procedure of this example with a carrier mixture free from isopropanol.

EXAMPLE 29 20 g. of the dyestuff sulfo-anthralinic acid+1-sulfotolyl-3-methyl-5-pyrazolone are pasted with 60 g. of water and dissolved with further heating in 870 g. of hot water. 10 g. of carob bean flour thickener pasted with a small amount of ethanol for better solubility, are addded to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50 and then 30 g. of a carrier mixture are added which consists of: 9 parts of nonylphenoxy acetic acid bis-,B-hydroxy-ethyl amide, 9 parts of the ammonium salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol.

Then 10 g. of 85% formic acid and 30 g. of water are added to this solution.

This pad liquor is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at 100 to 102. After steaming it is washed in about 40 warm water and then, at 40, in an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried. A yellow dyeing is obtained which has no sandwich effect.

When the carrier mixture used in the example is replaced by one of the mixtures Nos. (c) to (p) of Example 27 or by the carrier mixture used in Example 27 under (a), the procedure being otherwise the same as in Example 29, yellow dyeings are obtained which are free from any sandwich effect.

EXAMPLE 30 (a) 16 g. of the dyestuff sulfanilic acid 1-hydroxy[(3'- trichloropyrimidylamino) benzoylamino]naphthalene-3,

6-disulfonic acid are pasted with 40 g. of water and dissolved with further heating in 890 g. of hot water. 10 g. of galactomannan as thickening agent pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50, and 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. Then 10 g. of 85% formic acid and 30 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 100% calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated stream at 100 to 102. After steaming, it is washed with about 40 warm water and then, at 40, with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried. A red dyeing is obtained which has no sandwich effect.

EXAMPLE 31 13 g. of the 1:2 chromium-complex of the dyestuff 2- aminophenol 4 methy1-sulfone 1 acetylamino 7- hydroxynaphthalene are pasted with 60 g. of cold Water and dissolved with further heating in 890 g. of hot water.

10 g. of galactomannan thickening agent pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50, and then 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol.

10 g. of 80% acetic acid and 10 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woollen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 105% calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at 100 to 102. After steaming it is washed with about 40 warm water and then, at 40, with an aqueous solution containing 1 g./ liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried. A grey dyeing is obtained which has no sandwich effect.

Dyeings of a similar quality are obtained when the carrier mixture mentioned above is replaced by one of the mixtures Nos. (b) to (P) of Example 27, the procedure being otherwise the same as in Example 31.

EXAMPLE 32 13 g. of the chromium-complex of the dyestuff used in Example 31 are pasted with 60 g. of cold water and dissolved with further heating in 890 g. of hot water.

10 g. of galactomannan as thickening agent pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent the solution is cooled to 50, and then 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-p-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol.

10 g. of 80% acetic acid and 10 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 105% calculated on the dry weight of the goods. The slubbing is then steamed for 10 minutes in saturated steam at 100 to 102. Then it is treated for minutes in an aqueous bath of 95 containing 6 g./liter of 85 formic acid.

The slubbing treated in this way is washed with 40 warm water, then, at 40, in an aqueous bath containing 1 g./liter of nonylphenol polyglycol ether, and then rinsed and dried. A grey dyeing is obtained which has no sandwich effect.

When the carrier mixture used in the example is replaced by one of the mixtures Nos. (b) to (p) of Example 27, the procedure being otherwise the same as described in the example, grey dyeings are obtained which are free from sandwich effect.

EXAMPLE 33 37.5 g. of the 1:2-chromium-complex of the monoazo dyestuff 2-carboxy-l-aminobenzene 1-phenyl-3-methyl-5- pyrazolone and 5.0 g. of the 1:2-chromium-complex of the monoazo dyetsuff 2-aminophenol-4-sulfonic acid-N- methyl amidel-carbethoxyamino-7-hydroxynaphthalene are dissolved in an -warm mixture of 200 g. of a 2.5% aqueous galactomannan-solution, 270 g. of water and 30 g. of a carrier mixture consisting of 9 parts of nonylphenoxy-acetic acid bis-B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. The resulting solution is adjusted to a pH-value of 7 and diluted with cold water to 1000 parts. The temperature should be about 40.

This pad liquor is used to impregnate nylon toile which is squeezed to a liquor content of 50% of the fiber weight, steamed for 8 minutes at a temperature of 130, and rinsed first in hot and then in cold water.

A well-penetrated and very level olive dyeing is obtained.

EXAMPLE 34 A fabric consisting of 45 g. of wool and 55 g. of a blended fabric of 50% wool and 50% polyethylene glycol terephthalate fiber is impregnated and steamed analogous to the manner described in Example 31. The woollen fibers of the fabric are dyed grey while the polyester portion remains practically undyed.

EXAMPLE 35 A blended fabric consisting of 50% wool and 50% cellulose triacetate is impregnated and steamed analogous to the manner described in Example 31. The woollen fibers of the fabric are dyed grey while the triacetate portion remains practically undyed.

EXAMPLE 36 7 g. of the 1:2-chromium-complex of the dyestuff 2- amionphenol 4 methyl-sulfone 1-acetylamino-7-hydroxynaphthalene are pasted wtih 60 g. of cold water and dissolved with further heating in 690 g. of hot water.

10 g. of a thickening agent galactomannan pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50, and 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 9 parts of the di-fi-hydroxyethyl amine salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol.

10 g. of the moth deterrent of the formula I NHCONH- -Cl pre-dissolved in g. of warm water are added to this solution. The Whole is diluted with warm water to 990 g., and finally 10 g. of 80% acetic acid are added.

The p'ad liquor thus obtained is used to impregnate woollen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at 100 to 102. After steaming, it is washed with about 40 warm water and then, at 40, with an aqueous solution containing 1 g./

liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried.

A grey dyeing is obtained which does not show a sandwich effect and is well protected against damage by moths.

EXAMPLE 37 11 g. of the dyestuff of the formula NHCOCH; (1H

are dispersed in an 80 warm mixture of 200 g. of a 2.5% aqueous sodium alginate solution and 35 g. of a carrier mixture consisting of 9 parts of nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. The resulting solution is diluted with warm water to about 10 g.; the pH-value should be about 7.

The impregnation liquor thus obtained is used in Example 38 infra.

EXAMPLE 38 Polyethylene glycol terephthalate slubbing is impregnated at 30 with a pad liquor prepared according to Example 37 and is squeezed to a liquor content of 80%.

The slubbing is steamed for 30 minutes in saturated steam at 98, then it is washed with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with warm and cold water. A level yellow dyeing is obtained.

When the above pad liquor is mixed with 5 g. of ophenylphenol, the procedure being otherwise the same as described in example, a yellow dyeing is obtained which has higher color strength.

When the g. of the dyestufi? mentioned are replaced by the same amount of the dyestuff 1-amino-2-methoxy-4- hydroxyanthraquinone, the procedure being otherwise the same, as described in the example, a polyethylene terephthalate slubbing is obtained which is dyed red.

EXAMPLE 39 360 g. of the dyestuff 1 amino 6-nitr0-2-hydroxynaphthalene-4-sulfonic acid Z-hydroxynaphthalene in the form of a press cake are introduced in portions while stirring into a vessel fitted with a turbo-mixer and containing 360 g. of water. The mixture is stirred for one hour. 120 g. of a carrier mixture consisting of 9 parts of nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol are mixed with 10 g. of 80% acetic acid in a second mixing vessel. This homogeneous mixture is poured slowly while stirring continuously into the dyestuff suspension, and the whole is stirred for an other minutes until a homogeneous brown dyeing preparation is obtained which is ready for use.

A pad liquor is prepared by stirring 300 g. of this dyeing preparation with 350 g. of 60 warm water and 100 g. of a 2.5% aqueous carob bean flour thickener solu tion. The resulting solution is mixed "with 40 g. of chromium trifluoride and g. of 85% formic acid, and the liquor is then diluted with warm water to 1 liter. This liquor is used to impregnate woollen slubbing in the manner described in Example 18.

A level black dyeing is obtained, and the slubbing can be well combed and spun. The dyeing has good fastness to washing and light.

26 EXAMPLE 40 (a) 22 g. of the diazo dyestuff acid 2,2'-diamino-4,4 -diel1lor0diphenyl sulfide 3 2-arniuo-8-hydroxy-uaphthalenefi-sulfonic acid 6 g. of the dyestuff of the formula (3 NH2 m so n K/b CH3 H l O NH CH I CH3 CHZNHC O CHz-Cl and 13 g. of the chromium-complex of the monoazo dyestuff 2-amino-phenol 4 methyl sulfone 1-phenyl-3- methylpyrazolone (molar ratio of dyestulf to chromium=2: 1) are pasted with 60 g. of cold water. 750 g. of hot water are added while stirring and the whole is heated to boiling. The 10 g. of carob bean flour thickener pasted with ethanol for better solubility, are added while stirring. After the thickening agent has formed a clear solution, the solution is cooled to about 50, and 30 g. of a carrier mixture are added which consists of 16 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 8 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 8 parts of water and 3 parts of isopropanol.

This solution is combined as in Example 27, with 160 g. of an aqueous solution consisting of 40 g. of formic acid and 120 g. of water.

Woolen slubbing is dyed in the same manner as in Example 27.

Equally good dyeings without a sandwich effect are obtained by using instead of the carrier mixture employed in Example 40(a), equivalent parts of one of the following mixtures the procedure being otherwise the same as above:

(b) 16 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 16 parts of the potassium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 16 parts of water and 6 parts of isopropanol, or

(c) 16 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 32 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 32 parts of water and 12 parts of isopropanol, or

(d) 152 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-,B-hydroxyethyl amide, parts of water and 34 parts of isopropanol, or

(e) 24 parts of coconut oil fatty acid bis-B-hydroxypropyl amide, 10 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, 14 parts of water and 8 parts of isopropanol, or

(f) 136 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 38 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-B-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol, or

(g) 16 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 8 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-fl-hydroxyethyl amide and 8 parts of water, or

(h) 16 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 8 parts of the ammonium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide and 8 parts of potassium salt of sulfated myristyl alcohol pentaglycol ether.

EXAMPLE 41 (a) Example 28 is repeated, but in lieu of the 35 g. of the carrier employed therein, 35 g. of a carrier mixture are added which consists of 16 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 8 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 8 parts of water and 30 parts of isopropanol. 20 g. of 85 formic acid as well as a dispersion comprising 80 g. of water and 40 g. of chromium fluoride are added to this solution.

Padding is then carried out as described in Example 28.

A black woollen slubbing is obtained which has no sandwich effect.

A similar black wool dyeing without sandwich effect is obtained by using instead of the carrier mixture employed in Example 41(a) above, one of the following mixtures the procedure being otherwise the same a before:

(b) 153 parts of coconut oil fatty acid bis-p-hydroxyethyl amide, 8 parts of the sodium salt of sulfated coconut oil fatty acid mono-fl-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol, or

(c) 24 parts of coconut oil fatty acid bis-B-hydroxypropylamide, 10 parts of the sodium salt of sulfated (nonylphenyl)-(2,3dihydroxypropyl)-ether, 14 parts of water and 8 parts of isopropanol, or

('d) 136 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-,B-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

Equally satisfactory results are obtained by carrying out the procedure of the example with a carrier mixture which does not contain isopropanol.

EXAMPLE 42 (a) Example 29 is repeated but instead of the carrier used therein, 30 g. of a carrier mixture are added consisting of 153 parts of 'coconut oil fatty acid bis-B-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-,B-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol.

10 g. of 85% formic acid and 30 g. of water are added to this solution. Padding is carried out on wool as described in Example 29. A yellow dyed slubbing is obtained which has no sandwich effect.

A yellow dyeing without a sandwich effect on wool is also obtained when the carrier mixture employed in the example is replaced by one of the following mixtures the procedure being otherwise the same as before:

(b) 240 parts of coconut oil fatty acid bis-fi-hydroxypropyl amide, 100 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, 140 parts of water and 80 parts of isopropanol,

(c) 136 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-B-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

When the steaming period is extended from to or minutes, dyeings of a somewhat higher strength are obtained.

EXAMPLE 43 (a) Example 30 is repeated but instead of the carrier mixture used therein 30 g. of a carrier mixture are added which consists of 160 parts of coconut oil fatty acid bis-B- hydroxyethyl amide, 80 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 80 parts of water and 30 parts of isopropanol. 10 g. of 85% formic acid and 30 g. of water are added to this solution.

Woollen slubbing is then padded in the manner described in Example 30.

A red dyeing is obtained which has no sandwich effect.

A turquoise-blue dyeing is obtained when using instead of the 16 g. of the above dyestuif, 5 g. of sodium-copper phthalocyanin disulfonate, the procedure being otherwise the same as in the above example.

When the carrier mixture employed in the example is replaced by one of the following mixtures the procedure being otherwise the same as before, a red or a turquoise dyeing, respectively, is obtained which has no sandwich effect:

(b) 153 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 58 parts of the sodiumsalt of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, parts of water and 34 parts of isopropanol,

(c) 240 parts of coconut oil fatty acid bis-[i-hydroxypropyl amide, parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, parts of water and 80 parts of isopropanol,

(d) 136 parts of coconut oil fatty acid bis-(fl-hydroxyethyl)-amide, 68 parts of the ammonium salt of sulfated nonylphenoxy-acetic acid mono-fi-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol,

(e) 200 parts of nonyl-phenoxy-acetic acid bis-(13- hydroxyethyl)-amide, 100 parts of the potassium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ethcr, parts of water, and 80 parts of n-butanol,

(f) 130 parts of coconut oil fatty acid bis-(fl-hydroxyethyl)-amide, 70 parts of the sodium salt of sulfated (octylphenyl) (2, 3 -dihydroxypropyl) -ether,

(g) 150 parts of octylphenoxy-acetic acid bis(,8- hydroxyethyl)-amide, 120 parts of the sodium salt of sulfated nonylphenoxy-acetic acid bis-(B-hydroxyethyD- amide,

(h) 10 parts of nonylphenoxy-acetic acid bis-(fihydroxyethyl)-amide, 11 parts of the sodium salt of sulfated coconut oil fatty acid mono-p-hydroxyethyl amide.

EXAMPLE 44 (a) Example 31 is repeated but instead of the carrier mixture used therein 30 g. of a carrier mixture are added consisting of parts of coconut oil fatty acid bis-B- hydroxyethyl amide, '80 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 80 parts of water and 30 parts of isopropanol.

Then 10 g. of 80% acetic acid and 10 g. of water are added to this solution.

Woollen slubbing is then padded in the manner described in Example 31.

A grey dyeing is obtained which has no sandwich effect.

Dyeings of similar quality are obtained when the carrier mixture mentioned is replaced by one of the following mixtures, the procedure being otherwise the same as above:

(b) 153 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-fi-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol, or

(c) 240 parts of coconut oil fatty acid bis-fl-hydroxy propyl amide, 100 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, 140 parts of water and 80 parts of isopropanol, or

(d) 136 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-fl-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

EXAMPLE 45 A grey dyeing is obtained which has no sandwich effect.

A grey dyeing without sandwich effect is also obtained when the carrier mixture employed in this example is replaced by one of the following mixtures, the procedure being otherwise the same as before:

(b) 153 parts of coconut oil fatty acid bis-p-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-fl-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol, or

(o) 240 parts of coconut oil fatty acid bis-,B-hydroxypropyl amide, 100 parts of the sodium salt of sulfated (nonylphenyl)-2,3-dihydroxypropyl)-ether, 140 parts of water and 80 parts of isopropanol, or

(d) 136 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-fi-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

EXAMPLE 46 5.6 g. of the 1:2 chromium-containing monoazo dyestutf 2-carboxy-1-aminobenzene- 1-phenyl-3-methyl-5-pyrazolone and 5.0 g. of the 1:2 chromium-containing monoazo dyestuff 2-aminophenol-4-sulfonic acid-N-methyl amide1-carbethoxyamino-7-hydroxynaphthalene are dissolved in an 80 warm mixture of 200 g. of a 2.5% aqueous galactomannan solution and 30 g. of a carrier mixture consisting of 160 parts of coconut oil fatty acid bis-,B-hydroxyethyl amide, 80 parts of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl-amide, 30 parts of isopropanol and 350 parts of water. The resulting solution is adjusted to a pH-value of 7 and diluted with cold water to 1000 parts. The temperature should be about 40.

This liquor is used to impregnate nylon toile which is squeezed to a liquor content of 50% of the fiber weight, steamed for minutes at a temperature of 120 and then rinsed first in hot and then in cold water, steaming takes place in a pressure steam chamber.

A well-penetrated and level orange dyeing is obtained.

EXAMPLE 47 A fabric consisting of 45 g. of wool and 55 g. of polyethylene glycol terephthalate is impregnated and steamed in the manner described in Example 44. The woollen fibers of the fabric are dyed grey while the polyester portion remains practically undyed.

EXAMPLE 48 A blended fabric consisting of 50% of wool and 50% of cellulose triacetate is impregnated and steamed as described in Example 44. The woollen fibers of the fabric are dyed grey while the triacetate portion remains practically undyed.

EXAMPLE 49 Example 36 is repeated but instead of the carrier mixture used therein, g. of a carrier mixture are added consisting of 153 parts of coconut oil fatty acid bis-flhydroxyethyl amide, 58 parts of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol. 10 g. of the moth deterrent used in Example 36 are added in the same manner.

Woollen slubbing is treated with this pad liquor as described in Example 36.

A grey dyeing is obtained which has no sandwich effect and is well protected against damage by moths.

EXAMPLE 50 10 g. of the dyestuff of the formula NHCOCHa are dispersed in an 80 warm mixture of 200 g. of a 2.5% aqueous sodium alginate solution and g. of a carrier mixture consisting of 160 parts of coconut oil fatty acid bis-[i-hydroxyethyl amide, 80 parts of sulfated nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 80 parts of water and 30 parts of isopropanol.

30 The resulting dispersion is diluted with warm water to about 1000 g.; the pH value should be about 7.

The impregnation liquor thus obtained is used in EX- ample' 51 infra.

EXAMPLE 51 Polyethylene glycol terephthalate slubbing is impregmated with a pad liquor as prepared in Example 50, and is squeezed to a liquor content of The slubbing is steamed for 30 minutes with saturated steam at 98, washed with an aqueous solution containing 1 g./ liter of nonylphenol polyglycol ether and rinsed with Warm and cold water.

A level yellow dyeing is obtained.

When the above pad liquor is mixed with 5 g. of o-phenylphenol and the same procedure is used as above, a more intensive yellow dyeing is obtained.

When the 10 g. of the dyestuif mentioned are replaced by equivalent amounts of the dyestuff 1-amin0-2-methoxy- 4-hydroxy-anthraquinone the procedure being otherwise the same as described in the example, a red dyeing on polyethylene glycol terephthalate slubbing is obtained.

EXAMPLE 52 Example 39 is repeated, but instead of the carrier used therein, 120 g. of a carrier mixture consisting of 16 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 8 parts of sulfated nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 8 parts of water, and 3 parts of isopropanol, which 120 g. of carrier have been mixed together with 10 g. of 80% acetic acid in a separate mixing vessel, are added under continuous stirring to the dyestuif suspensions, and the whole is stirred for another 15 minutes. In this manner, a homogeneous brown dyeing preparation is obtained which is ready for use.

The pad liquor is obtained by diluting 300 g. of the above dyeing preparation with 350 g. of warm water at 60 and 100 g. of an aqueous 2.5 carob bean flour thickening solution. The resulting solution is mixed with 40 g. of chromium trifluoride and 20 g. of formic acid, and the liquor is diluted to 1 liter with warm water. This liquor is used to impregnate woollen slubbing in the manner described in Example 41.

A level black dyed slubbing is obtained which can be well combed and spun. The dyeing has good fastness to washing and light, and is free from sandwich effect.

EXAMPLE 5 3 (a) 25 parts of a red dyestuff of the formula 2.5 parts of an orange chromium complex dyestuff of the formula:

and 6.25 parts of blue dyestuff of the formula:

ii NH-CH 1 CH3 (EHrNH-CO 011201 are dissolved in 500 parts of hot water and 200 parts of a 5%-aqueous thickener consisting of etherified carob bean gum, and 40 parts of a mixed anionic/non-ionogenic dye assistant consisting of a mixture of 45% of sodium lauryldiethylene-glycol sulfate, 45% of coconut oil fatty acid N,N-bis-ethanol-amide and of isopropanol, are added to the resulting solution. Thereto 100 parts of a 10% formic acid solution are then added and the whole is made up with water to 1000 parts. The temperature should be 40 C.

Wool slubbing is impregnated wit-h the resulting 40 warm solution and squeezed out so as to leave 100% by weight of dye liquor on the slubbing, calculated on the weight of the latter. The slubbing is then treated in the horizontal steam station of an apparatus as shown in the accompanying drawing which comprises a 700 mm. high pre-fixing chamber, a curved duct section, the curvature of which describes an angle of about 60 against the vertically disposed central axis of the pre-fixing chamber, and a subsequently arranged second fixing chamber, which is provided with a conveyor belt, the part of the upper reach of which extends horizontally from the discharge opening of the curved duct section to the discharge means at the end wall of the second fixing chamber is about2 80 cm. long and the upwardly inclined end part of which upper reach is about 45 cm. long and rises at an angle of 34. The padded slubbing is introduced into the prefixing chamber at a speed of 5 meters per minute without contacting any part of the pre-fixing chamber. The slubbing passes through this chamber under its own weight during 8 seconds without touching any part of the pre-fixing chamber and is subjected therein to saturated steam having a temperature of about 98100 whereafter the pre-steamed slubbing is laid into folds in the curved duct section. The folded material advances under its own weight towards the exit of the curved portion, the 60-" curvature of said portion causing the horizontal folds to be gradually tipped into a near vertical position in Which they remain on the upper reach conveyor belt, being transported through the second fixing chamber, for about 20 minutes; when passing upward on the inclined upper reach portion, they are tipped lightly backward upon the succeeding folds, whereby they are easily lifted off the conveyor belt by the discharging roll.

The second fixing chamber is also filled with saturated steam of about 98100 C., while the folded goods pass therethrough.

Thereafter, the thus treated slubbing is withdrawn from the second fixing chamber, washed with water in the back washing machine and air-dried.

The slubbing is now dyed a uniform, dark red color which shows no sandwich effect and is approximately of standard depth 1.

When Example 53(a) is repeated with carriers outside the scope of the invention, 'but chemically related to individual carrier components falling under that scope, unsatisfactory results are obtained, as shown by the following Examples 53(b) to (f).

(b) By repeating Example 53, but using, instead of the dye assistant used therein, an equal amount of a similar dye assistant consisting of a mixture of 30% by weight of the condensation product of coconut oil fatty acid and diethanolamine in a molar ratio of 1:2, 21% of lauric acid N,N-bis ethanol-amide, 24.5% of N-methyl-N-fi-hydroxyethyl-ammonium laurate and 24.5 of sodium lauryl triethylenoxy-sulfate, and otherwise following the same procedure, there is obtained an uneven, red dyeing showing a distinct sandwich effect and more bluish hue than that obtained by Example 53.

(c) By repeating Example 53, but using instead of the dye assistant given therein 40 parts of sodium nonylphenol diethylenoxy sulfate there is obtained an even dyeing in a bluish shade, which, however, shows a distinct sandwich effect.

(d) By repeating Example 53, but using instead of the dye assistant given therein an equal amount of the condensation product of nonylphenol and ethylene oxide in a molar ratio of about 1:15, there is obtained an uneven dyeing showing a distinct sandwich effect and which has a strong shade shift toward blue, compared with that obtained in Example 53.

(e) By repeating Example 53, but using instead of the dye assistant given therein, an equal amount of the condensation product of lauryl alcohol and ethylene oxide in a molar ratio of about 1:8 there is obtained an uneven dyeing with distinct sandwich effect.

(f) By repeating Example 53, but using instead of the dye assistant used therein, an equal amount of the product obtained by condensation, at to 200", of coconut oil fatty acid and diethanolamide in a molar ratio of 1:2, there is obtained, after a short treatment, a full, uneven dyeing with dyestutf precipitation on the material due to the formation of a very pronounced coacervate in the padding liquor.

EXAMPLE 54 Example 53 is repeated, using nylon 66 slubbing in lieu of wool slubbing, and 5 parts of the 1:2 chromium complex of the dyestuff of the formula in lieu of the dyestuff used in Example 53. The slubbing passes at a speed of 7 meters per minute through the prefixing zone and remains for 10 minutes in the second fixing chamber. Steam conditions in both zones are the same as in Example 53. The color depth of the resulting red dyeing is somewhat higher than in the case of Example 53.

EXAMPLE 55 Example 53 is repeated but the dyestuff used therein is replaced by 5 parts of the dyestuff of the formula SOzCH COOCH3 '6 The wool slubbing passes at 'a rate of 7 meters per minute through the pre-fixing zone and is steamed for 10 minutes in the second fixing chamber. A flawless light grey dyeing is thus obtained.

EXAMPLE 56 By repeating Example 53, but using instead of the dye assistant used therein 30 parts of a mixture obtained from 35 parts of sodium nonylphenol diethyleneoxy-sulfate and 15 parts of coconut oil fatty acid, N,N-bis-;8-hydroxy ethyl-amide, practically the same product is obtained as that of Example 53.

EXAMPLE 7 By repeating Example 53, but using instead of the first component of the dye assistant given therein an equal amount of sodium lauryl sulfonate there is obtained a level dyeing free from sandwich etfect and of about 60% greater depth of shade than that of Example 53.

EXAMPLE 58 20 parts of chromium dyestufi of the formula:

(SE HO are dissolved in 400 parts of hot water. To the resulting solution are added 200 parts of aqueous 2% carob bean flour solution as thickener and 30 parts ofthe dye assistant used in Example 53. To the whole are added 200 parts of an aqueous l0 %-acetic acid and the resulting liquor is diluted to a volume of 1000 parts by the addition of water. The temperature of the liquor is raised to 45. Nylon 66 slubbing is impregnated with this solution and squeezed out to retain a 110% dye liquor absorption. Then the same steaming procedure as in Example 53 is followed. The material is washed in the lback-washing machine in a known way, and then dried.

A very level, well fixed brilliant red dyeing is thus obtained.

EXAMPLE 59 By repeating Eaxmple 58, but using instead of the dye assistant given therein, an equal amount of 35 parts of sodium nonylphenol-diethyleneoxy-sulfate and 15 parts of coconut oil fatty acid N,N-bis-B-hydroxyethyl-amide and instead of the acetic acid, 20 parts of ammonium sulfate, equally good red dyeings are obtained.

EXAMPLE 60 By repeating Example 58 but using instead of the second component of the dye assistant given therein an equal amount of the product obtained by condensing, at ISO-200, coconut oil fatty acid and diethanolamine in a molar ratio of 1:2, there are obtained similarly satisfactory level red dyeings.

EXAMPLE 61 By repeating Example 58 but using instead of nylon 66 slubbing, nylon 66 tow, a level red dyeing is obtained on said tow.

34 EXAMPLE 62 By repeating Example 58 but using instead of nylon 66 viscose towel, a level red dying is obtained thereon.

EXAMPLE 63 -By repeating Example 53, but using in lieu of the dye assistant given therein an equal amount of the product obtained by condensing; at l50-200, coconut oil fatty acid and diethanol amine in a malor ratio of 1:2, there is obtained an equally good blue dyeing on nylon tow.

EXAMPLE 64 4 parts of the dyestutf of the formula P-a romOsmoOan 4% N 2 parts of the dyestutf of the formula HO NltCO S 0 3N8 0 3N8 and 2 parts of the dyestuff of the formula fl) IIIH CH H |O3N8 CH SO NB.

I NH CH;

are pasted with 20 ml. of cold water and further diluted with 480 ml. hot water to a thin solution which had been brought to the boil were subsequently added 400 ml. of a 2% galactomannan stock solution. After cooling to about 50 C., =20 parts of a carrier mixture consisting of the sodium salt of sulfated lauryl alcohol diglycol ether [C H (OC H -OSO Na], coconut oil fatty acid N,N-bis-(p-hydroxy-ethyl)-amide and isopropanol in a weight ratio of 9:9:2, and finally 20 ml. of formic acid previously diluted with water to 80 ml. were added. Water is then added to make the 'whole up to a volume of one liter. The addition of the various ingredients is done with constant stirring. Wool slubbing is padded with this liquor, squeeed to leave a pick up of and steamed for 20 minutes with saturated steam of 98- 100" C. After washing on a back-washer unit to remove thickener and chemicals and subsequent drying, a slubbing of even beige shade free from sandwich effect is obtained.

EXAMPLE 65 Similar results are obtained when repeating Example 64, but using in lieu of the dye assistant used in that example, the same amount of the dye assistant used in Example 63.

35 36 EXAMPLE 66 2 parts of the dyestufi of the formula and 1 part of the dyestuff of the formula CH5 OH J sczcrr,

c CH 0 1 Q0 ONH N=N-cH-o O-NHNHC 0-JJHN=N v CH 6 CH i S O H H are dissolved in 250 parts of hot Water and mixed with The slubbing is then treated in the back-washing ma- 100 parts of an aqueous 2% 'carob bean flour thickener chine at a speed which allows contact with a coppering stock solution. To the resulting mixture, 5 parts of the dye bath to last for at least seconds. assistant used in Example 53 are added and the whole is A very satisfactory level light tan shade is obtained. brought up to a volume of 1000 parts by the addition of water. The temperature of the liquor is brought to 45. EXAMPLE 67 Viscose slubbing is impregnated with this liquor, squeezed out to retain a 100% liquor absorption and then steam-treated in the apparatus which is described in Example 53. In this apparatus, the slubbing has a travel Similar results are obtained by repeating Example 66, but using, in lieu of the dye assistant used therein, 5 parts of the dye assistant used in Example 59.

rate. of 6.5 meters per minute in the prefix-ing chamber and remains in the second fixing chamber for 15 minutes, EXAMPLE 68 saturated steam of a temperature of 98-100 being Example 66 is repeated, but instead of the dystuff applied in both treatment chambers. blend used therein, 20 parts of a dyestufi of the formula O H I HaN- S 0 11 H 0 8 NH:

COOH

i COOH HOOCCHzO COOH are used and steam-treated, the goods passing at a rate of 4.5 meters per minute through the pre-fixing chamber and being steamed for 30 minutes in the second fixing chamber; saturated steam of 98-100 is used in both chambers. In all other respects the procedure is the same as that used in Example 66, and similar dyeings of navy blue shade and equally satisfactory properties are obtained as in that example.

EXAMPLE 69 Example 68 is repeated, but parts of the dye assistant used in Example 59 are used in lieu of the dye assistant used in Example 66. Similar satisfactory results are obtained.

EXAMPLE 70 Example 66 is repeated, but in lieu of viscose slubbing,

viscose tow is dyed, with similar satisfactory results.

EXAMPLE 71 Viscose tow is dyed by strictly following the procedure of Example 70 but using 5 parts of the dye assistant used in Example 59 is lieu of the dye assistant used in Example 66. Similar results as in Example 70 are obtained.

EXAMPLE 72 Viscose tow is dyed by strictly following the procedure of Example 68, and goods of similar satisfactory navy blue shade are obtained.

EXAMPLE 73 Viscose tow is dyed by strictly following the procedure of Example 69, and goods of similar satisfactory navy blue shade are obtained.

We claim:

1. A dyestulf paste consisting essentially of (I) from about 8 to 35% by weight, calculated on the total weight of the paste, of a non-cationic dyestuff capable of drawing on the respective fibers to be pad dyed, from a pad liquor having a pH in the range of 2 to 10,

(II) from about 5 to 25% by weight, calculated on the total weight of the paste, of a carrier mixture consisting essentially of '(A) an unsulfated amide of a member selected from the class consisting of wholly saturated fatty acid of from 8 to 14 carbon atoms, and lower alkanoic acid which is substituted by higher alkyl-phenoxy wherein the higher alkyl moiety has from 8 to 12 carbon atoms, amidified with a member selected from the group consisting of (a) mono-hydroxy and di-hydroxy substituted mono-alkylamines of from 2 to 4 carbon atoms, having one hydroxyl group in w-pOsition,

(b) bis-(w-hydroxyalkyl)-amines of a total of from 4 to 6 carbon atoms,

(c) N-lower alkyl-N-w-hydroxyalkylamine wherein the hydroxyalkyl group has from 2 to 3 carbon atoms, and

(d) mono-(w-alkoxy-alkyD-amine of a total of from 3 to 5 carbon atoms, at least two of which pertain tothe alkyl moiety;

(B) a member selected from the group consisting (i) a sulfated alkanol of from 8 to 14 carbon atoms,

(ii) a sulfated condensation product of an alkanol of from 8 to 14 carbon atoms with ethylene oxide, condensed with each other in a molar ratio of from 1:1 to 1:20,

(iii) a sulfated condensation product of alkylphenol, the alkyl moiety of which has from from 8 to 12 carbon atoms, with ethylene oxide, in a molar ratio of from 1:1 to 1:20,

(iv) a sulfated N-hydroxy-lower alkyl-substituted amide of a substantially wholly saturated fatty acid of from 8 to 14 carbon atoms,

(v) a sulfated (higher alkylphenoxy)-substituted lower alkanoic acid N-hydroxylower alkyl-substituted amide, wherein the higher alkyl group from 8 to 12 carbon atoms,

(vi) a sulfated (higher alkylphenyl)-(2,3-dihydroxypropyl)-ether the higher alkyl radical of which has from 8 to 12 carbon atoms.

(vii) a sulfated hydroxy-substituted unsaturated fatty acid or a lower alkyl ester thereof, said fatty acid having from 15 to 18 carbon atoms,

(viii) the alkali metal, ammonium, lower alkylammonium and w-hydroxy-lower alkylammonium salts of (i) to (vii) inclusive, and

(C) a member selected from the group consisting of lower alkanol of from 2 to 4 carbon atoms and fl-alkoxyethanol of a total of from 3 to 8 carbon atoms, the proportions by weight of (A) to (B) ranging from about 5:1 to 1:5, and the content of (C) ranging from 0 to 20% by weight, calculated on the total weight of said mixture,

(III) from 0% to such weight percentage of a pH- adjusting agent compatible with the aforesaid paste constituents as is sufficient for adjusting the pH of said paste to a value compatible with the dyestuff defined under (I) and maintaining homogeneity of the paste,

(IV) from 0% to a sufficient weight percentage of thickener to impart to the paste a viscosity in the range of from 1 to 50 poises,

(V) from 0 to about 10% by Weight of an adjuvant selected from the group consisting of ethylene glycol, thiodiethylene glycol, glycerin, urea and thiourea, and

(VI) an adequate amount of water to attain the aforesaid viscosity range,

all percentages being calculated on the total weight of the paste.

2. A dyestuif paste in accordance with claim 1 wherein the amount of the adjuvant defined under .(V) is 0%.

3. A dyestuff paste in accordance with claim 1 wherein the carrier mixture (II) consists essentially of a (A) an unsulfated amide of an acid selected from the class consisting of substantially Wholly saturated fatty acid of from 8 to 14 carbon atoms, and lower alkanoic acid which is substituted by higher alkylphenoxy wherein the higher alkyl moiety has from 8 to 12 carbon atoms, amidified with a hydroxy-lower alkyl amine;

(B) a member selected from the group consisting of 

